Chemistry of thiocarboxylates: Synthesis and structures of neutral silver(I) thiocarboxylates with triphenylphosphine †

A series of trialkylammonium salts of indium and gallium thiocarboxylates, [Et 3 NH][M(SC{O}Ph) 4 ]?H 2 O (M ~In 31 (1), Ga 31 (2)) and [n-Bu 3 NH][In(SC{O}Ph) 4 ] (3), [R 3 NH][In(SC{O}Me) 4 ] (R ~Et (4) and n-Bu (5)) have been synthesized and characterized. The structure of 2 has been determined by single crystal X-ray diffraction and was found to be isomorphous and isostructural with [Et 3 NH][In(SC{O}Ph) 4 ]?H 2 O (1) reported earlier.Thermal properties of 1-5 were studied. Compound 4 exhibits a phase transition which was characterized by DSC. Thermogravimetric and pyrolysis experiments of 1, 3, 4 and 5 showed the formation of tetragonal b-In 2 S 3 while 2 yielded poorly crystalline monoclinic Ga 2 S 3 . Thin films of tetragonal In 2 S 3 were obtained on a Ni coated Si substrate by MOCVD experiments using 1. Under similar conditions, 2 resulted in a film containing both cubic c-Ga 2 S 3 and hexagonal Ni 0.96 S. When a Cu coated Si substrate was used 1 deposited thin films of tetragonal CuInS 2 , while 2 furnished a mixture of tetragonal Cu 1.96 S and tetragonal CuGaS 2 films. The composition of the thin films also depends on the temperature employed during the growth process. The composition, stoichiometry, phase analysis and surface morphology of the thin films obtained have been unequivocally characterized using XRD, SEM, TEM, RBS, Selective Area Electron Diffraction and XPS. It appears that the decomposed product(s) of 1 and 2 react with the substrate to form the metal sulfide thin films.

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“…This is a common feature observed in various thiobenzoate complexes. 26,[31][32][33][34][35][36][37][38] Thermal properties of compounds 1-5…”

Section: Description Of the Molecular Structure Ofmentioning

confidence: 99%

Trialkylammonium salts of [M(SC{O}R)4]– (M = Ga3+ and In3+) as precursors for metal sulfide thin films

et al. 2003

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“…19 Our interest in studying the dppm adducts of coinage metal thiocarboxylates stems from the systematic research we have been carrying out on the chemistry of thiocarboxylates. [19][20][21][22][23][24][25][26][27][28] We recently revealed the ability of thiocarboxylates to display µ-S, µ-S, O, µ 3 -S 2 , O and µ 3 -S 3 bonding modes in triphenylphosphine copper thiocarboxylate compounds. 19 Surprisingly, the chemistry of the triphenyl- † Electronic supplementary information (ESI) available: variable temperature 31 P NMR spectral data.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structures and 31P NMR studies of bis(diphenylphosphino)methane adducts of copper and silver thiocarboxylates †

Deivaraj

Vittal

2001

J. Chem. Soc., Dalton Trans.

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The compounds [Cu 3 (µ-dppm) 3 (SC{O}Me) 2 ][PF 6 ] 1, [Cu 3 (µ-dppm) 3 (SC{O}Ph) 2 ][X] (X = ClO 4 2 or PF 6 2a) were synthesized by treating Na ϩ R{O}CS Ϫ (R = Me or Ph) with a mixture of [Cu(MeCN) 4 ]X (X = PF 6 or ClO 4 ) and bis(diphenylphosphino)methane (dppm) in stoichiometric ratios. The structures of 1 and 2 have been determined by single crystal X-ray crystallography. The trinuclear core is held intact by the three bridging dppm ligands and two capping thiocarboxylate anions. One of the thiocarboxylate anions triply bridges to the Cu 3 (µ-dppm) 3 core through a µ 3 -S and the other by a µ 3 -S,O bonding mode.] 4 were prepared by treating Na ϩ R{O}CS Ϫ (R = Me or Ph) with dppm and the corresponding silver salt. The structures of 3 and 4 were determined by X-ray crystallography. Both the thiocarboxylate anions bond in µ-S fashion, thereby stabilizing the trinuclear core. In all the four crystal structures C-H ؒ ؒ ؒ O hydrogen bonding is present between one of the methylene hydrogen atoms and the carbonyl oxygen of the thiocarboxylate ligand. 31 P NMR studies in solution at low temperatures reveal that all the compounds retain their trinuclear core in solution, while intramolecular exchange involving dppm does not cease even at lower temperatures. Attempts to prepare monocapped trinuclear cations, [M 3 (µ-dppm) 3 (SC{O}R)] 2ϩ , and binuclear neutral compounds, [M 2 (µ-dppm) 2 (SC{O}R) 2 ], yielded only the corresponding bicapped trinuclear compounds.

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“…The coordination mode for the dtp ligands is bimetallic-biconnective (l 2 :g 2 , mode IV). The average AgÁ Á ÁAg distance of 3.8 Å, is much longer than that reported (3.3 [26]. Although S(1) bridges Ag(2) and Ag(1) atoms almost symmetrically, S(3) bridges Table 1 Bond lengths (Å) and angles (°) for compounds 1-4, 5a 0 , 7, and 8.…”

Section: Synthesismentioning

confidence: 76%

The influence of alkane spacer of bis(diphenylphosphino)alkanes on the nuclearity of silver(I): Syntheses and structures of P,P′-bridged clusters and coordination polymers involving dithiophosphates

Liu¹,

Sarkar²,

Liaw³

et al. 2009

Journal of Organometallic Chemistry

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Chemistry of thiocarboxylates: Synthesis and structures of neutral silver(I) thiocarboxylates with triphenylphosphine †

Cited by 35 publications

References 33 publications

Trialkylammonium salts of [M(SC{O}R)4]– (M = Ga3+ and In3+) as precursors for metal sulfide thin films

Trialkylammonium salts of [M(SC{O}R)4]– (M = Ga3+ and In3+) as precursors for metal sulfide thin films

Synthesis, structures and 31P NMR studies of bis(diphenylphosphino)methane adducts of copper and silver thiocarboxylates †

The influence of alkane spacer of bis(diphenylphosphino)alkanes on the nuclearity of silver(I): Syntheses and structures of P,P′-bridged clusters and coordination polymers involving dithiophosphates

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